Production of coloring matters



Patented Mar. 24, 1925.

UNITED STATES PATENT OFFICE.

ARTHUR HUGH DAVIES, DECEASED, LATE OF WIL'LENHALL, ENGLAND; BY MARYoLIvIA' DAVIES, ADMINIsTnATmx, or FRASER THOMSON, or GARLISLE, ENGLAND,

L, ENGLAND; AND ROBERT ASSIGNORS To SCOTTISH DYES LIM- ITED, OFGARLISLE, CUMBERLAND COUNTY, ENGLAND.

PRODUCTION OF COLORING MATTERS.

No Drawing.

To all whom it may concern.

Be it known that we, MARY OLIVIA DAvms, administratrix of the estate ofthe late ARTHUR HUGH DAVIES, a subject of the Kin of Great Britain andIreland, and resi 'ng at 72, New Road, W'illenhall, 1n the county ofStafi'ord, England, and ROBERT FnAsnR THoMsoN, a subject of the King ofGreat Britain and Ireland, and residing at Murrell Hill Works, Carlisle,in the county of Cumberland, England do hereby declare that the saidARTHUR UGH DAVIES, deceased, and ROBERT FRASER THOMSON have inventedcertain new and useful Improvements in the Production of ColoringMatters, of which the following is a specification.

This invention relates to the production of coloring matters either as(1 es or inter- 2 mediates for the production of yes.

It has for its object to provide an improved or new series of suchcoloring matters. We have made a large number of experiments and havefound a new series 2 of oxidation products which can act as dyes orintermediates for the production of- The basis of these products may bere? garded as substituted dibenzanthrones, this term including forexample dimethyl-dibenzanthrone and dinaphthalimide, all of which bodiesmay be considered to contain a ketonic perylene group, that is to say,the perylene nucleus with other pairs 0 ring formations joined to theperylene nucleus at positions indicated by 3 :4 and 3' :4 and WhlCl'lhave in these additional ring formations at least one ketonic group,that is, the whole molecule contains at least one pair of ketonicgroups; Dibenzanthrone itself would be included in this latterdefinition, for which reason we refer to the basis of the new series ofoxidation products as substituted dibenzanthrones.

We have also found that these oxidation products are ca able of beingreduced, but not necessarily ack to the parent body, by

such substances as sulphites.

We have also found that these oxidation products form compounds withsulphuric,

Application filed August 24, 1923. SerialNo. 659,234.

acid which can be used as a means of isolatmg the required bodies asthese sulphuric acid compounds are readily decomposed on treatment withexcess of water giving products in a form suitable for use in furtherreactions or themselves as dyestufls.

The accompanying diagram represents in a conventional manner what may beregarded as the constitutional formulae of dibenzanthrone, the perylenering system being shown in heavy lines.

In'the followin table a list is given of some of the oxidation productsaccording. to the present invention, together with the colour of thebody in strong sulphuric acid, and the colour of cotton dyed with theproduct from an alkaline hydrosulphite bath.

Our invention in brief consists in the production of dyes orintermediates by the oxidation of a substituted dibenzanthrone. 8

The following examples are given to illustrate method for the productionof oxidation products of bodies containing a perylene nucleus Ewample 1.

10 parts of purified dibenzanthrone dissolved in 200 parts of sulphuricacid, 66 B., and 5 parts of crystalline boric acid are treated with 10parts of manganese di-' 'oxide and 20 parts of sulphuric acid, 66 B., atsuch a rate that the temperature rises to (3., at which temperature thewhole is then kept for one hour. The oxidation product is isolatedaccording to well-known methods. This dyestuff gives a dull olive erineare dissolved along with 5 grcy-blue on making acid.

Example I I The oxidation products in general may be purified bytreatment with strong sulphuric acid in the particular manner. describedfor the oxidation product of dibenzanthrone below 10 parts of theoxidation product of dibenzanthrone in the state of fine powder aredissolved in 400 parts of strong sulphuric acid at 60 C. The correctamount of water is now added to the solution to reduce the concentrationof the sulphuric acid to 85%. After allowing to stand for 12 hours themixture is filtered and washed with sulphuric acid of the same strength.The precipitate consists of a pure form of the oxidation product, and isworked up by diluting with water, boiling up, reducing with sodiumbisulphite and filtering.

The purity of the product can be demonstrated by dye tests, and it isfound that shades are obtained of a bright yellow-olive colour,considerably more brilliant and intense than can be obtained from thecrude produe. The acid filtrates containing a further quantity ofconsiderably less pure oxidation product.

The shades obtained from the latter are considerably duller and weaker.c

E mample I l l 10 parts of the dyestufi obtained by the fusion withpotash of the condensation product of 2-chloranthraquinone withglycparts of crystalline boric acid in 350 parts of strong sulphuricacid. To the solution are added 12 parts of manganese dioxide, thetemperature being then raised and maintained at 60 for several hours.

The product is then worked up by diluting with water, boiling up,reducing with sodium bisulphite and filtering. After washing the productconsists of 40 parts of paste of a dull brown colour, which gives instrong sulphuric acid a solution unaffected by copper, and giving agreen precipitate on dilution.

It dyes cotton blue shades, which are not fast' to the action of acidsor alkalies.

Example I V.

phuric acid. 7 parts of manganese dioxide are then added and thesolution is then raised to and maintained at 60 C. for two hours.

The product is worked up by the usual method as described in ExampleIII.

The product consists of 25 parts of a dark yellowish brown paste, whichgives-in strong sulphuric acid a brilliant red violet colour, and on theaddition of water, gives first a brown sulphuric acid compound, and onfurther dilution, a yellow-olive precipitate.

.The product dyes cotton from the hydrosulphite vat yellow-olive shades,which are not fast to the action ofacids and alkalies.

In the preparation of the oxidation products described above we havementioned the use of manganese dioxide and sulphuric acid, but otheroxidizing agents such as nitric acid can be employed with suitableresults. The parent bodies containing the perylene nucleus may also benitrated, reduced, diazotized and boiled to form oxycompounds thatbehave in general similarly to those described above.

Having now described our invention, what we claim as new and desire tosecure by Letters Patent is 1. Oxidation products of substituteddibenzanthrones.

2. Oxidized and subsequently reduced derivatives of substituteddibenzanthrones.

In testimony whereof we have signed our names to this specification.

MARY OLlVIA DAVIES, Adwiim'stmtrim of Arthur Hugh [ht v7 0.9,

deceased.

ROBERT FRASER THOMSON.

